The high pressure-high temperature structural stability of Zeolite A (ZA) has been studied using the X-ray diffraction (XRD) method. Structural studies at high temperatures show a reduction in the oxygen occupancy, belonging to the water molecule, indicating thermal dehydration and subsequent expulsion of water molecules from the pores of the structure. ZA does not undergo structural phase transition with temperature. However, structural transitions are observed in in situ XRD studies at high pressure and high temperature. At 1.3 GPa and 300 °C, the cubic ZA concomitantly transformed to cubic sodalite (SOD) and tetragonal zeolite NaP (ZNP). This transition was completely forbidden at 2.7 GPa, where a temperature-induced amorphization was favored at 250 °C. The thermal studies at higher pressure reveal the marginal influence of pressure on the thermal expansion coefficients of hydrated ZA. Pressure evolution of the high pressure-high temperature phases indicates no further phase transitions up to 5.9 GPa. The equation of state fit to the pressure-volume data of these phases show that ZNP is less compressible, followed by SOD and ZA. In contrast to the behavior at 0.1 MPa, SOD shows a pressure-induced negative thermal expansion (NTE) at 5.9 GPa. On the other hand, the positive thermal expansion (PTE) observed along the direction of c axis is compensated by the NTE along the a axis leading to a negligible volume thermal expansion for the ZNP structure. The bulk moduli and thermal expansion coefficients of all of the observed phases are reported. The outcomes of this study have been consolidated as a pressure-temperature phase diagram, which provides an insight into the technological and industrial applications of ZA at extreme conditions.